Textile material and method of dyeing the same



Patented June 13, 1933 UNITED STATES PATENT OFFICE cmnmrcn 28. WHITE,

or MON'I'CLAIR, NEW JERSEY, ASSIGNOR T vIvATnx PROOESSES, II IG., LOIDI,NEW JERSEY, A CORZPORAIION OF NEW JERSEY TEXTILE Merriam AND mnTHoD orDYEIN'G THE sum 't. v No Drawing. Driginal application filed April 16,1924, Serial No. 706,884. Divided and this application filed November 7,1927. Serial No. 231,7?2."

. The invention which forms the subject of the present application. (adivision of my copending application Serial No. 706,884, filed April 16,1924, now Patent No.- 1,648,433,

issued November 8, 1927) relates to waterduce a dyed textile materialwhich will be highly resistant or repellent to fungus growth andbacterial attack, and which will be more repellent to water and lesssubject to shrinkage than materials dyed by the commonly used processes.

- Another important obj ect of the invention is to produce or depositwithin or upon the fibres of the textile material, prior to. orsimultaneously with the d eing operation, insoluble compounds orsubstances of a basic character which shall be capable of absorbing orneutralizing acidic substances or acid radicals which may develop fromthe molecular dissociation (under the influence of light, heat,moisture, or radiant energy) of the color compounds or the color lakes.with which the textile material is dyed; to produce or deposit upon orwithin the fibresof the textile material, compounds or substances whichhave strong alfinity for the acidic ions that may be liberated throughthe action of the agencies noted above and which, once united with theseacidic ions, hold them tightly and are not readily dissociatedtherefrom, thereby preserving the fibres from the tendering whichinevitably results when such ions are free to unite with or attack thecellulose of the fibre.

A still further important object of the in:

vention is to provide a method of produc- One obupon or within the ingor depositing compound, within or upon the fibres, prior to orsimultaneously with the dyeing opera-' 1 Another important object of theinvention" is to incorporate organic dyestufi's or dyeing media withinthe bodyof mineral dye or water or fungus-repellent compounds orsubstances referred to above, to the end that such dyestuffs, coloringmedia or color lakes thus enclosed shall be more or less protected fromthe influence of atmospheric agencies,

heat, light, and moisture, and will thereby be rendered faster to lightand also more resistant to fading in washing.

The objects above mentioned are achieved in the present invention by theuse, in. or upon the fibres of the suitable metal compounds, preferably.of metals of the rare earth group and, in some cases, by the use ofchromium, aluminum,

magnesium, and titanium. Among the rare textile material, of

the protecting compound I or substance, or the fungus or water repellentearth metals usable are cerium, neodymium,

praseodymium, lanthanum, yttrium and erbium. Thorium may be used also,and in using the term rare earth metals hereinafter I mean to includethorium therein. These metals possess the important property of beingprecipitated as hydroxids when their compounds are acted upon byalkaline sulfids. these hydroxidswhen formed or precipitated fibres oftextile material impart marked water-', mildew-, and bac teria repellentproperties, and, in addition,

many of the hydroxids have strong and defi-Y chromium hynite colors. Forexample, droxid 1s graylsh green, cerium h droxid is Many ofyellowishwhite, neodymium hy roxid has a reddish tone, pras'eodymium hydroxid haseen and erbium hydroxid a purple-red color. Thehydroxids of theseelements are. i

all strongly basic, as are also their carbonates,

and are in a high degreecapahle of neutraliz ing acids. While alkalinesulfids precipitate hydroxids of the above mentioned metals, on

, preclpitated as sulfids, some and chromium.

' upon the fibre,

rately or combined'together.

the other hand copper, nickel, cobalt, antimony, iron, cadmium, andmanganese are of which have high tinctorial value. Thus antimony sulfidis orange in color, cadmium sulfid is yellow, and copper sulfid blackishbrown. Such colors are, in general, more decided than those of thecorresponding hydroxids, and when mixed in varying proportions arecapable of producing varied tones and shades of a wholly mineralcharacter. But nearly all the sulfids are capable of more or less easyoxidation to sulfates, which latter, because of their solubility, may bereadily washed out, or because of their tendency to dissociate maylibcrate acidic ions which react upon and hy-' drolyze the cellulose ofthe fibres u on which they may have been precipitate thereby tenderingthe fibres and eventuall rendering the -fabr1c1 useless. It is there oreof the highest importance to have present, in or basic elements orcompounds, as forexample an insoluble hydroxid, which will neutralize ordestroy acidic ions as rapidly as'the latter may be formed and set free.

The presence of the insoluble rare earth compound (usually an hydroxid)renders the textile material repellent to water and to fungus andbacterial growth, as explained in my copending application Serial No.639,219 filedMay 15, 1923.

Some of the sulfids referred to above (for example antimony, fids) arewhen dry considerably resistant to oxidation, and especially so whenthey are occluded or embedded in a mass of basic ma terial, or areprotected from atmospheric agencies by water repellent coatings ornonabsorbent and repellent compounds such as copper, antimony, nickel,cobalt, and iron, chemical reaction or-p'rocess that produceshydroxidsfof the rare earth metals and hydroxids of aluminum, titanium,magnesium sulting color is a blend of wholly mineral origin, possessingthe intrinsic 'fastness of mineral colors to light. Many of the shadesthus produced are unique, and the colors may "be further. varied bvarious admixtures of tin, antimony, or ca ium sulfids, usedsepa- Thedestructive eifect of sulfuric acid ions can also be avoided, ormeasurably and substantially diminished,.by the use of insolublediflicultlysolublecompounds of the alkali earth metals, as calcium,strontium and barium, or the related magnesium, among which compoundsmay be mentioned hydroxids, carbonates, tannates, and insolubleorganiccompounds in general. Such compounds have a very strong afinity for thesulfuric acid ion,

cadmium and co per sulas sulfids in the same treatment to effect suchafter-treatments almost invariably have an In many such cases the redand once united therewith release are very diflicult of dissociationtherefrom. With the exception of magnesium, they have the advantage thatthe compounds formed with sulfuric acid are very insoluble, bariumsulfate being one of the most insoluble com pounds known.

n The scope and utility of the'invention are not limited to theproduction and application of the so-called mineral dyes, but on thecontrary the invention admits of a wide extension and application to thefield of sub stantive and adjective dyeing in which organic coloringmedia are also used. This is strikingly illustrated in the field ofdirect dyes, and especially the so-called sulfur dyes,

where the coloring medium is dissolved in and applied with a strongsodium sulfid solution or other alkaline sulfid solution. If the sulfurdye be applied in an alkaline sulfid bath to a fabric alreadyimpregnated with a and substances already noted, the sodium sulfid orother alkaline sulfid will decompose the impregnating salt, forming aninsoluble hydroxid, which hydroxid will, as it is formed, be thoroughlypermeated by the color medium, occluding it in a colloidal or gelatinousmass which when dry strongly protects it from light. or radiant energyin general and from atmospheric agencies. The action is not essentiallydifferent when used with certain mordant dyes, such as for to; pro uceor deposit; upon or withinthe the metalllc soaps and hydroxlds of theclass fi alluded to, and I have found it practicable to precipitatecadmium,

bres, compounds which render the textile material strongly repellent towater and milunnecessary, in most cases, any drastic afterpurposes. Suchappreciable, and in some cases a ver.

am'aging effect upon the colors and of the dyed material.

great shaded duction dation or breakin down of thecolor molecule (as insulfid-dyed material, for example) it is not always necessary,.in myinvention, that tain or carryncompounds of a strongly basic character.other cases the" requ rements of fast color non-tendering of the fibres,etc.,

are met by the presence of aninsoluble compound which occludes orenvelops the dolor dew and to bacterial attack, thereby making Exceptwhere there is danger of the proof acid radicals or ionsthrough oxi-'soluble salt of one or more of the elements the fibres of the textilematerial also conrial advantageous wate'r-, bacteria-' andfungus-repellent properties but also furnish the necessary mordant formordant dyes. These insoluble compounds are formed and precipitated bythe action of alkaline fluorids, phosphates, borates, etc., and in manycases the precipitating solutions can be added directly to the dye bath,so that when textile material previously impregnated with soluble rareearth metal compounds is passed through the,

baththe latter compounds will be converted into insoluble compoundssimultaneously with, and as a part of, the actual dyeing opmy process asble salt of a metal or element capable of being insolubilized ashydroxid by reaction withalkaline hydroxide, carbonate or sulfide. Forthe purpose of coloring the textile material the impregnating solutionalso contains a salt of a metal capable of being precipitate as ametallic sulfide of suitable color or tint by reaction with an alkalinesulfide. Among the salts capable of being converted into insolublehydroxides I may mention chloride, acetates, and nitrates of the rareearth elements; and as examples of salts capable of being converted intoinsolublesulfides which.

also are capablev of dyeing the textile material, I may mention any salt(preferably sulfur-free) of iron, copper, nickel, cobalt, cadmium,antimony, and bismuth. The following are excellent formulas-forimpregnating baths: w

' Percent Water- 50 @opper acetate; .25. liars-earth metal acetate oracetates 25 (b) 1.

Waten 50 Copper acetate 16 Chromium acetate 18 Rare earth acetate oracetates 16 Both the above solutions when treated with sodium sulfide orother alkaline sulfide as a precipitant .yield a mineral dye of an olivedrab color, the shade being darker with a greater amount of copper andlighter with a greater amount of chromium or rare earth,

rial passes into the dye bath the alkaline sulbonate as theprecipitating I precipitants,

bath I sometimes rial) and hence a large variety of shades can beobtained by proper proportibnin of these two ingredients. he alkalinesulde treatment also precipitatesupon or in'the fibres of the textilematerial the rare earth metal in the form of insoluble hydroxide, which,being strongly basic, serves to neutralize any acid ions that may be setfree by subsequent dissociation of the copper or chromium sulfide in themanner previously-alluded to, thereby protectin the fibres from injuryby the ten-. dering 'e ect which such ions or radicals would otherwisehave. The impregnation can be effected at ordinary temperatures, byimmersing the textile material in the selected solution, Ion enough(usually-momentarily) for thoroug impregnation. The material can then bedried, with or without the use of heat, and treated with the selectedprecipitating bath, which may be a solution of sodium sulfide of, say,from Sto 20 per cent strength, at practically any temperature up toboiling, according to the nature of the fibre; cotton, for exam le,permitting a high temperature, while sil requires a relatively lowtemperature. 7

Many dyestuffs are, or can be, applied in a strongly alkaline bath.Notable among these are the direct dyes known as sulfur dyes, which aresoluble only in'a strong solution 0 an alkaline sulfide; and dyes of themordant I type, and their prototypes,

the madder dyes.

In using a dye of these classes, I first impregd nate the textilematerial with any soluble salt (preferably an acetate) of a metal whichcan be recipitated in insoluble form by alkaline sul des, hydrates orcarbonates. For this purpose I pre though I can use salts of othermetals,-as aluminum,'magnesium, chromium and titanium, Afterimpregnation the. textile material is dried, and is then ready for thealkaline dyebath. In the case of sulfur dyes, as the matefide therein,usually sodium sulfide, reacts with the soluble salt with which thematerial has been impregnated andconverts it into the insoluble hydroxidpre'ci itates, and at the same time carries into t e ap arentlycolloidal precipitate on the fibre t e color base of the dye-bath. Inthe case of alizarin, madder and other dyes requiring alkaline baths, Iprefer to use caustic soda or sodium carhowever, should not be used fortextile material impregnated with an aluminum com und.

f as

fer salts of the rare earths medium. These After yeing cotton with analkaline dye treat it with a soap solution, for the urpose ofbrightening andfurther fastenmg the color. In such case the soap reacts(afterwashing the mate- Y with the metallic compound on the fibre,forming an insoluble soap which rendersthe fabric repellent to water.

Preferably the 130 gus growth; as for example the rare earth dyeing, andin the subsequent dyeing of the metals, especially thorium, cerium,didymium and lanthanum.

In the case of dyes which cannot be applied from an alkaline but requirea neutral or an acid bath, I first impregnate the textile materialwith'a rare earth element, notably thorium, cerium, lanthanum ordidymium, in the form of a compound (as for example an acetate) fromwhich a compound can be precipitated which is insoluble or but slightlysoluble in dilute acids such as are used in acid impregnated material Iinclude as a precipitant in the acid dye-bath a fluorid, phosphate,

benzoate, salicylate, or other suitable salt pf an alkali metal oralkaline earth metal Their as a result of the reaction betwcenthe saltor salts just named and the rare earth salt the latter is converted intoan insoluble compound-a fluorid, phosphate, etc, as the case may be,with the same effect'as is produced in the case of dyes requiringalkaline baths as described above.

Cotton exhibits no basic properties, and hence cannot be dyed by meansof certain acid colors which are available for animal fibres, and thechoice of dyestuffs for use with cotton is therefore much more limitedthan in the case of animal fibres, for example wool and silk, whichlatter occupies an intermediate position between cotton and wool. Ingeneral, cotton dyeing is confined to the following classes ofdyestuffs:

1. Basic colors. (salts of organic bases). the dyeing power of whichlies wholly in the basic portion of the salt and requires an acid or anacid salt to develop the color. These dyes require a mordant.

2. Direct colors, the characteristic feature of which is that they dyecotton directly, without mordanting. These colors fall into two distinctgroups, which are known as direct cotton colors and sulfid colors. Theyare mostly alkali salts of sulfonated tetrazo bases, formed bydiazotizing benzidine or diamido-stilbene, and then uniting the productswith amines or phenols. Such dyes are thus already alkalin or at leastare of the nature of alkaline salts and are not incompatible with otheralkaline bases.

As an application of my invention to the dyeing of cotton with directdyes the following example may be given:

The cotton is first impregnated with a rare earth salt or salts, as forexample cerium acetate. The impregnating solution may also contain, forexample, a soluble chromium salt,

' say chromium acetate, for the purpose of increasing fastness to lightand washing. The impregnated cotton is preferably dried, after iteratesmay be of the composition:

l/vater 1 gallon Dye (direct color or colors) 5 oz. Sodium fiuorid 6 oz.Sodium carbonate oz.

The amount of dyestufi is variable, especially since the absorption bythe fabric is in inverse proportion to the amount of dye liquor in thedye bath. The sodium carbonate can be replaced by the same amount ofsoap. When the impregnated material is passed into the dyeing andprecipitating bath the sodium fluoride converts the rare earth metalsalt on the fibres into an insoluble fiuoride; and carries into thefibre, and into the fluoride precipitated thereon, a certain portion ofthe dyestuif. The sodium fluoride may be replaced by any other saltcapable of producing a like effect, as for example sodium, potassium orammonium phosphate, benzoate, salicylate, silicate, hydroxide when notincompatible withthe dyest uif), carbonate, cyanid, etc.

The sulfur colors canb'e applied only in a strongly alkaline bath, acircumstance that limits them, practically, to cotton, linen, jute, andother vegetable fibres. The usual sol-= vent for the dye is a strongsolution of sodium sulfide. In applying my inventionwith this class thetextile material is first impregnated with soluble salt of one or moreof the metals heretofore mentioned fora like purpose. Preferably, butnot necessarily, the salt'(is one of an acid which has no tenderingeffect when dried, as for example an organic acid, say acetic or lactic.The impregnated fabric, preferably dried, is passed into the sulfur dyebath, thereby converting the soluble metallic salts of the impregnatedfibre into insoluble compounds, as for example hydroxides. At the sametime the color medium dissolved in the bath is released by thedecomposition of the sulfide and appears intimately incorporated withthe amorphous colloidal or quasi-colloidal hydroxide precipitated on andwithin the fibre. If desired, the conver sion of the soluble salt intoan insoluble compound can be effected before dyeing, in which case theyeing operation may proceed exactly as with an unimpregnated fabric, butthe ancorporation of the dye is not likely to be 45 to water or mildewor both.

' cent.

' the textile material is,-as

' at the same time,

- der consideration have the power of comb usable for the purpose,

Mordantcolors possess the property of combining with metallic oxides andother I compounds, the combination, in general producing the tint, whichvaries with the particular oxide or compound employed. Others of thisclass possess, within themselves, the property of dyeing, irrespectiveof their ability to formcolor lakes with metallic oxides. The chemicalexplanation of this class characteristic is found in the fact that themembers of the class all contain hydroxyl groups while others containboth hydroxyl and car boxyl groups. It is not, however, necessary thatthe metallic base exist in the textile material in the form of oxide orhydroxide, inasmuch as the color media of the class un- 1ning witholeates, tannates, silicates, etc., to form the lake on or within thefibre. In applying my invention with mordant colors in the case of thedyes already described, first impregnated with the desired metallicsalt, preferably an acetate, and is then dried or tightly squeezedbetween rollers to eliminate at least the major portion of the moisture.The dried or squeezed fabric is next passed through the dye bath, whichlatter contains in addition to the color medium or media a chemicalagent capable of precipitating and rendering insoluble the metallic saltor salts with which the material. was impregnated. Among theprecipitating or insolubilizing agents I may mention hydrates andcarbonates of the alkali metals, alkaline-silicates, oleates, tannates,borates, oxalates, fluorids, phosphates, etc. In this way the necessarymordanting, that is, the formation of the color lake, is efiecte'd, and

as in the other cases hereinbefore described, a substance is introducedinto the textile material, in or upon the fibres thereof, which rendersthe latter repellent Developed colors include a group of colors whichare developed upon the fibres by the successive ap lication of theirconstituent parts, one 0 which is usually of an acid Y character. Inapplying my invention with a dye of this class the metallic compoundwhich is'precipitated upon or'in the fibre must be of such nature thatit will not readily dissolve in dilute acids. Such compounds are wellillustrated by the phosphates of the rare earth metals(includinghypophosand the fluorids of the same group, as wellassilicates and, to a lesser extent, the dried hydroxides. The latterare, as arule, very soluble in the freshly precipitated wet state, butmany, as for instance thorium and cerium hydroxides, are renderedrelatively insoluble'by drying. Zirconium hydroxide precipitated from ahot with neutral or alkaline dye-baths.

solution is almost insoluble 'in dilute acid I solutions, although thehydroxide formed by cold precipitation is easily soluble in suchsolutions. The acids used to develop the colors in the dyeing operationare'quite dilute and hence there is little or no danger of dissolvingthe metallic compound with which the textile material'has been imregnated;

The most striking example o'fthis sub-group .is the well knownparanitranilin red.

(b) Developed direct aol'ora-These "are developed from primuline or fromdirect colors containing free amido compounds by passing the dyedmaterial into a solution of an amine or a henol. (0) Benzo-mtrolcolora-With these the material is dyed by means of certain direct colorswhich are developed by assing the textile material into a solution 0diazo compounds, as for instance .diazotized paranitranilin. The processis similar tothe development of the insoluble azocolors. I

In dyeing operations in which the. actual dyeing'is conducted in analkaline bath, the

fixing or precipitating agent'required for insolubilizing thewater-repellent or mildewrepellent compound or compounds may be ingeneral directly incorporated with the dyebath and the insolubilizingoperation is then carried on simultaneously with the dyeing of thetextile material. When the dye-bath is of a neutral character theinsolubilizing can also be effected simultaneously with the dyeing, butfor this purpose a neutral precipitant fluoride, phosphate, oleate,silicate, etc. With the exception of the developed dyes, such as theinsoluble azo 'dyes and their" related groups, nearly all cotton dyeingis efiected With silk and wool the case is different, these materialsbeing usually dyed in an acid bath, and in this case the fixing orprecipitating agent for insolubilizing the water-repellent ormildew-repellent compound must be such that the compound so producedshall be relatively insoluble acid dye bath. the rare earth in generalconfer mildew-repellency as ,well as affording a basis for building upwater- These conditions are met by repellency. Typical examples ofprecipitated compounds (of rare earth elements) which are relativelyinsoluble in-dilute acids oleates, stannates and tannates,

in the dilute acidity of the Y and in somev element compounds, which isnot limited to the (deposited upon thorough, approximating in fact thethorough penetration so characteristic of yarn or stock dyeing, and theresult is therefore relatively faster to light and washing.Nevertheless, where the simultaneous method is not practicable onaccount of the incompatibility of the insolubilizing media and the.

dye-bath, the fabric or other textile material can be madewater-repellent or mildewor bacteria-resistant before dyeing and maythen be dyed by any of the well known methods. It is important,however,-where the dyeing is to be carried out with an acid bath, totake precautions that the compound or within the fibres) by which theresistant or repellent properties are imparted to the material, shall beof such nature that it is relatively insoluble indilute acids. Althoughthe simultaneous method is to be preferred, the subsequent dyeing methodis equally efiicacious in preventing the staggering of .colors which isalmost inevitable in former processes in which an already dyed materialor fabric is subjected to treatment for the purpose of rendering itrepellent to water or resistant to bacterial attack.

I do not claim herein I ble salts or other componds as media for protecting textile material from tenderingproducts resulting from theaction of atmospheric or other agencies on the coloring agent; 'nor do Iclaim for such pounds of elements (as for example calcium, strontium,barium, and zinc) which are capable of forming sulfids in the wet way.Such compounds in solution react to form sulfids when the textilematerial is treated with alkaline sulfid, and the sulfide so produced inthe textile material not only have no protective effect but may even insome cases be themselves a source of damage to the material. In the termcompound of an alkali metal, and the like, in the appended claims, Iinclude ammonium compounds as equivalents.

It is to be understood that the invention specific details hereindescribed but can be de ned by the following claims.

I claim- 1. The method of coloring textile mate-' the use of Water-solu;

purposes the use of com-" carried out in other wags without departurefrom its spirit as to those imparted terial attack, or tending products,comprising impregnating the textile material with a soluble compound ofa metal selected from the class consisting of thorium and the cerite andytterite earth metals, capable of conversion into a compound having thesaid repellent property and treating the impregnated textile materialwith a solution of a compound of an alkali metal adapted to effect suchconversion and containing a dyestufi", whereby the compound of theselected metal is converted intoan insoluble compound having the saidrepellent property and the dyestuff is deposited in or upon the textilematerial. i

2. The method of coloring textile material with organic dyestufl's andrenderingv the same repellent to fungus growths, bace terial attack, ortendering products, comprising impregnating the textile material with asoluble compound of a-metal selected from the class consisting ofthorium and the cerite and ytterite earth metals, capable of conversioninto a compound having the saidrepellent property, and treating theimpregnated textile material with a solution containing a dyestufi'compound which will react with the said metal compound to precipitate aninsoluble compound of the metal, whereby the dyestufi and a solublealkali metal is deposited in or upon thetextile material I and theconverted into a condition of insolubility in water, in the saidsolution, and in subsequent solutionsused for treating the saiddyestuff.

The-.method of coloring textile material and rendering the samerepellent to fungus growths, bacterial attack or tendering' products,comprlsingimpregnating the textile material with a soluble salt of ametal selected from the class consisting of the rare earth metals,capable of conversion into a compound having the said repellentproperty, and treating the impregnated textile material with a solutionof a compound of an alkali metal capable of efiecting said conversion,said solution containing an organic dyestufi', whereby the selectedmetal is converted into a compound insoluble in the said solution or insubsequent solutions which could be used to treat the said dyestufi andthe dyestuff is deposited in or upon the said textile material.

4. The method of rial and rendering the same repellent to fungusgrowths, bacterial attack, or tendering products, comprisingimpregnating the textile material pound of a metal selected from theclass consisting of the rare earth metals and a commg of chromium,aluminum, magnesium and titanium, capable of conversion into a compoundhaving protective properties similar by compounds of thGc'fiI'SfGcompound of the selected metal is 4 with a solution of a cominto acondition of insolubility in water and v in the second solution and thedyestufi'is deposited in or upon 'the textile material.

5. The method of coloring textile material and rendering the samerepellent to fungus growths, bacterial attack and tendering products,comprising impregnating the textile material with a soluble salt ofthorium, and by treating the impregnated material with a solutioncontaining an'organic dyestufi" and a suitable compound of an al-' kalimetal converting the thorium salt into a compound insoluble in thetreating solutior. or in subsequent solutions which could be used to thedyestufi in or upon the textile material.

6. A. method as described in claim 5, in which the thorium salt isacetate.

7. A method as described in claim 5, in which the thorium salt isacetate and the alkali solution is a solution of sodiumsulfid,

whereby the thorium acetate is converted into thorium hydroxid.

8. The method of coloring textile material and rendering the samerepellent to subsecomprising colorquent tendering products, ing thetextile material with a dyestufl in a suitable vehicle and depositing inthe textile material a substance serving to protect the textile materialfromsaid tendering products, said substance consisting of a compound ofan element selected from the class consisting of chromium, aluminum,magnesium, ti-

tanium, and the rare earth metals, incapable of forming a sulfid in thewet way, said compound being insoluble in water and in the vehicle bywhich the said dyestuif is applied.

9. The method of coloring textile material and rendering the samerepellent to subsequent tendering products, comprising simultaneouslycoloring the textile material with a dyestufi in a suitable vehicle anddepositing in the textile material a substance serving to.

protect the textile material from said tendermg products, saidsubstanceconsisting of a compound of an element selected from the classconsisting of chromium, aluminum,

-. magnesium,

' ing hydroxide of a metal titanium, and the rare earth metals,incapable of forming a sulfid in the wet way, said compound beinginsoluble in water and in the vehicle by which the said dyestuii isapplied. i

1'0. Textile material organic dyestufi and containing aneutralizselected from the class consisting of thorium and the ceriteand ytterite earth metals, m at least organic dyestufi' organic dyestufitreat the dyestuti and depositing.

.- pound ofan element selecte colored withan insoluble in water'and onesolution by which the dyestufi could be applied to textile material.

11. Textile material-colored with a sulfur dyestufi and containing aprotective neutralizing compound of an element incapable of forming asulfid in the wet way, said compound being insoluble in water and in atleast one solution by which the dyestufi could be applied to textilematerial.

12. Textile material colored with a sulfur dyestuii and containing aneutralizing hydroxid of a rare earth metal, insoluble in at least onesolution by which the dyestufi could be applied to textile material.

13. Textile material colored with an and containing thorium hydroxid. v

14. Textile material colored with an and containing a protectivecompound of a rare earth metal, said compound being insoluble in waterand in at least one solution by which the dyestufl could be applied totextile material.

15. Textile material colored with a sulfur.

rotective comfrom-the class consisting of chromium, aluminum, magnesium,titanium, and the rare earth metals, said compound being insoluble inwater and in at least one solution by which thedyestufi could be appliedto textile'material.

In testimony whereof I hereto afiix my signature.

CLARENCE B.

dyestufi and containing a

